RE VIEW PAPER
13
C NMR Spectroscopy of Coumarin Derivatives
Helmut Duddeck* and Manfred Kaiser
Ruhr-Universitat Bochum, Abteilung fur Chemie, Postfach 102148, D-4630 Bochurn 1, FRG
The 13C chemical shifts of 209 naturally occurring and synthetic coumarin derivatives are listed and a number
of methods for signal assignments are explained. Substituent effects on "C chemical shifts (SCS) in
monosubstituted coumarins and non-additivities of SCS in coumarins with more than one substituent are
discussed in detail.
Since the early 1970s, 13CNMR spectroscopy has
developed into one of the most valuable tools for
structural elucidation of organic compounds and
natural products. Although often a wealth of
information-particularly in stereochemical aspects-
can be extracted from the 13C spectral parameters,
their evaluation is sometimes still difficult for non-
specialists, so that misinterpretations may lead to er-
roneous conclusions.
Therefore, a number of surveys have been published
in books1-" and journals"-17 summarizing the results
of 13CNMR investigations in various fields of natural
product chemistry. Naturally occurring coumarins,
however, have been neglected in this respect, although
they represent an important family of compounds in
nature." Their data are still scattered in the literature,
apart from one article4 in which a number of highly
substituted coumarins were described, but so far there
is no systematic compilation. This may be one reason
why most publications dealing with the isolation and
chemical investigation of coumarin derivatives ignore
13CNMR analysis, despite its potential.
Therefore, we decided to review the 13CNMR liter-
ature of coumarin derivatives, not only to improve the
method's reputation in this field, but also to call
readers' attention to some precautions which should
be followed in order to avoid errors. Finally, we wish
to encourage those who are working with coumarins to
record and publish the I3C NMR spectral data of their
compounds, because there are still large gaps to be
filled.
METHODS FOR SIGNAL ASSIGNMENTS
In general, 13CNMR spectra are recorded under
proton-noise (broad band) decoupling" in order to
avoid the severe signal overlap which can easily occur
because of the large one-bond carbon-hydrogen cou-
pling constants (ca. 120-250 Hz). This procedure re-
sults in a breakdown of all signal splittings due to such
* Author to whom correspondence should be addressed
CCC-00304921/82/002(M055$09.00
0Wiley Heyden Ltd, 1982
couplings. Owing to the low natural abundance of the
13C isotope (ca. 1.1'/0), 13CNMR signals appear as
narrow singlets if no further NMR-active nuclei with
high natural abundance (e.g. 19F or 31P) are present in
the molecule.
This spectral simplification, however, produces a
serious drawback in signal assignments since valuable
coupling information is destroyed. Thus, a variety of
assignment methods have been developed, and those
which are the most significant for coumarin derivatives
will be introduced in this section.
There are five main areas: experimental NMR
techniques, coupling constants, solvent effects, shift
reagents and derivatization.
Experimental NMR techniques
These techniques consist mainly of 'H decoupling
methods, some of which are surveyed briefly in this
section.
The most prominent is the single-frequency off -
resonance decoupling (SFORD) p r o ~ e d u r e , ' ' . ~ ~
whereby the decoupler frequency is positioned outside
the 'H resonance range (off-resonance, Fig. lb). Thus,
all carbon-hydrogen couplings are reduced to such an
extent that only the largest coupling constants [namely
'J(CH)] give rise to small residual splittings (.Ir), from
which the number of hydrogens adjacent to the re-
spective carbon atoms can be read directly: singlets
correspond to quaternary carbons, doublets to
methine, triplets to methylene and quartets to methyl
groups. Nevertheless, in these spectra, signal overlap
and second-order effects sometimes prohibit unam-
biguous interpretations in unfavourable cases.
New techniques, such as the recording of J-coupled
spin echoes21a and INEPT,21bhave recently been de-
veloped to circumvent these difficulties. By a simple
excitation sequence, which can be executed routinely
by most advanced PFT-NMR spectrometers, the in-
formation about the number of adjacent hydrogens is
not reflected in residual signal splittings but in signal
phases and intensities;21a C and CH2 signals appear as
positive and those of CH and CH, as negative singlets
ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982 55
 H. DUDDECK AND M. KAISER

Since residual coupling constants, J,, are linearly

related to the difference, Au, between the proton
Larmor frequency, uH, and that of the decoupler field,
u2, under certain condition^'^.^^
Au
J, = J(CH) * - (if y H 2 >>Au)
YH2
the off -resonance decoupling method can be extended
by sequencing the decoupler frequency through the

r
proton resonance range at low power.26 Graphical
evaluation of the J, vs. Au relationship allows the
determination of carbon-hydrogen correlations in the
molecule under investigation.26
Another variant is selective single-frequency proton
d e c o ~ p l i n g Irradiation
.~~ of a given proton signal in
the ' H N M R spectrum causes a collapse of the signal
splittings for the directly bonded carbon atom only,
whereas all other carbon signals are still more or less
broadened owing to their couplings.

Coupling constants

Carbon-hydrogen coupling constants are useful aids

for peak assignments in the 13CNMR spectroscopy of
coumarin derivatives. A simple train of consecutive
FID recordings without decoupling is, however, disad-
vantageous. The gated decoupling method27 is, rather,
recommended whereby delays are inserted between
successive recordings during which the decoupler is
switched on. This technique yields a considerable
signal-to-noise ratio improvement, because the nuc-
lear Overhauser effect (NOE)24 is regained (Fig. 2).
Further, larger pulse durations are allowed which, at
least in part, compensate the loss of time due to the
decoupling delays.
Peak assignments by observing 13C-'H coupling
constants have been described in various publications
dealing with the I3C NMR of ~ o u m a r i n s . ~ , ~ ~ - ~ ~
Figure 3 gives the 'J(CH) values for coumarin (1)28
and psoralen (159).37In the first instance all values are
within a small range (about 163-165.5 Hz), except for

160 150 140 130 120

I I I I I

Figure 1. 13C NMR spectra of coumarin (1): (a) proton-noise

decoupled; (b) SFOR decoupled; (c) J-coupled spin echo meas-
urement with a delay time T = 1 / J = 6 ms ( J = 166.7 Hz); (d) as
in (c) but ~ = ( 1 / 2 ) J = 3 m s .

(b)

(Fig. l(c)). The parameters may even be adjusted in

such a way that only the signa!s of quaternary carbons
appear in the spectrum (Fig. l(d)). This is of great value,
since these are often of very low intensity owing
to saturation effects (long spin-lattice relaxation
times, T,) and/or low nuclear Overhauser enhance-
m e n t ~ , so
~ ~that
- ~they
~ can be hidden below the much
more intense signals corresponding to hydrogen- Figure 2. Proton-noise decoupled (a) and gated decoupled2' (b)
bearing carbon atoms. 13C NMR spectrum of coumarin recorded at 62.9 MHz.

56 ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982

 13CNMR SPECTROSCOPY OF COUMARIN DERIVATIVES
03:"
164.3 6 /
162.9 164.3
2 0
179.7
3 .
7 \
164.3 ~
165.3
(a)
Figure 3. One-bond carbon-hydrogen coupling constants of (a)
coumarin (1)28and (b) psoralen (159).37
C-3, which has the only value larger than 170 Hz. This
was used to differentiate between C-3 (6 = 115.2) and
C-8 (6 = 115.1) in coumarin (l).35 The same pattern
was found for a variety of derivatives; only for couma-
rins bearing a 4-hydroxy group is J(C-3, H-3) consid-
erably ~ r n a l l e r . ~ ~ . ~ ~ ~ ~ ~
In f u r a n o c ~ u m a r i n s(Fig.
~ ~ 3b), the largest 'J(CH)
values appear in the furan moiety, that for C-2' even
exceeding 200 Hz.
Carbon-hydrogen couplings via more than one bond
have also been investigated intensively, and have
proved to be very useful for signal correlation^.^'-^^^^^
Three-bond couplings, 3J(CH) for example, depend on
the geometry of the molecular moiety; they are gener-
ally larger in transoid than in cisoid orientation^.^^.^^
Thus, the assignment of the C-2 and C-2' signals of
3-carboxycoumarin (8) was a c c o m p l i ~ h e d(see ~ ~ Fig.
4).
Even if the "J(CH) values ( n > 1) cannot be deter-
mined exactly owing to second-order effects, the signal
shapes often give helpful hints.40 Giinther et ~ 1 . ~ '
established a fingerprint rule for ortho-disubstituted
benzenes, by which a- and P-methine carbon signals
can be distinguished. This rule can be employed suc-
cessfully for the distinction of the C-5 and C-6 signals
of coumarin derivative^.^'
In one instance the method of biosynthetic label-
was applied to synthesize I3C-enriched
aflatoxin B1, which contains a coumarin moiety.4245
In these papers several assignments were assisted by
the enhanced signal intensities and by the one-bond
carbon-carbon coupling constants, 'J(CC).
H" 0
\ ences a small upfield shift. An enhanced contribution
J (C-2, H-4) : 10.3 Hz (transoid)
I/ (C-2',H-4) : 5 . 4 Hz (cisoid)
Figure 4. Three-bond carbon-hydrogen coupling constants in
3-carboxycoumarin (8).35
Solvent effects
The I3C shielding is not very sensitive to solvent
changes. Although coumarins contain a polar lactone
164.3
7 2
162.7
\
, a 172.1
residue, the I3C chemical shifts of coumarin and its
derivatives remain constant within about *1 ppm
when the deuteriochloroform solvent is replaced by
deuterated dimethyl s u l p h o ~ i d e ,despite
~ ~ , ~ ~the differ-
8
0 ent complexing abilities of these two solvents. Thus,
167.2
only if small substituent effects on the I3C chemical
(b) shifts (SCS) are to be discussed is it advisable to record
all spectra in identical solvents.
Basically, this also holds for protic organic solvents.
Gottlieb et uL40 found that the addition of methanol to
a deuteriochloroform solution involves very constant
signal displacements for coumarins, which may be
used for assignments: C-2, 4.30 f 0.10; C-3, -0.09 *
0.08; C-4, 1.19*0.14; C-5/C-6/C-7/C-10, 0.58*
0.10; and C-8/C-9, 0.27 f0.05 ppm. Since, however,
these values are so small, this rule should not be
overemphasized.
Similar, although much more pronounced effects
were reported by S ~ j k a , who~ ~ , compared the 13C
chemical shifts of a number of coumarin derivatives in
chloroform and in 96%. sulphuric acid. For coumarin
itself the differences are: C-2, 13.2; C-3, -5.3; C-4,
16.5; C-5, 4.3; C-6, 7.1; C-7, 8.0; C-8, 3.4; C-9, 0.6;
and C-10, 3.7ppm, when the data of the chloroform
spectrum are subtracted from those in sulphuric acid.
Even the 'J(CH) values are sensitive, and vary up to
16 Hz.
These dramatic effects are explainedz9 by protona-
tion of the carbonyl group and by considering different
mesomeric forms of the molecule. They are not con-
stant in their magnitude, however, when coumarin is
substituted in different positions.29 This finding, and
the uncertainty whether the molecule under considera-
tion will survive such treatment (96% H,SO,), de-
creases the merit of this procedure.
Shift reagents
Another possibility of producing explicable signal dis-
placements is the addition of complexing reagents.
Bose et ~ 1 reported
. ~ ~that titanium tetrachloride in
deuteriochloroform can be used as a shift reagent in
'H and 13CNMR spectroscopy, and applied this
method to coumarin and some furanocoumarins (ang-
elicin derivative^).^'
Figure 5 demonstrates strong downfield TiC1,-
induced shifts for the carbonyl and the P-carbon in the
enone chromophore, while the a-carbon signal experi-
3.0 / \ -1.4
1.6 \
0
-
0.5 0.6-'
21) -0.1
(a)
Figure 5. TiCI,-induced 13C NMR signal shifts of (a) coumarin
(1) and (b) the furanocoumarin 189.48
ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982 57
 H. DUDDECK AND M. KAISER
Figure 6. The dipolar rnesorneric form of cournarins.
of the dipolar mesomeric form, I1 in Fig. 6, has been
offered47 as an explanation for this result. Moreover,
distinct shifts of the C-6 and C-7 signals are observed
and, also, for C-10, but only for the furanocoumarins.
This method clearly deserves further attention; the
induced shifts, however, are obviously dependent on
substitution, so that a detailed exploration is required.
The use of lanthanide shift reagents (LSR) to simp-
lify NMR spectra and for structure determinations was
recognized in the early 1 9 7 0 ~Although ~ ~ it was
shown that contact contributions are generally not
negligible in I3C NMR,5",51 this complication can be
overcome by using ytterbium c o m p l e x e ~ In . ~ this
~~~~
case contact shifts are essentially restricted to carbons
directly bonded to the complexation site.
It is amazing that apart from one, and even then an
' data on the lanthanide in-
indefinite e ~ a m p l e , ~no
duced shifts of the 13C signals of coumarin derivatives
seem to have been published. A study reporting the
application of LSR to the ' H N M R spectroscopy of
c o u m a r i n ~indicates
~~ the position of the europium ion
in the coumarin-Eu(fod), complex to be as shown in
Fig. 7.
Figure 7. Geometry of the coumarin-Eu(fod), complex.53
The 19 and d values do not vary too if the
coumarin molecule bears substituents at the benzene
moiety only. With substituents at C-3, however, the
coplanarity of the lanthanide ion and the molecular
plane of the substrate can no longer be assumed.54
Derivatization
Another method is to compare the 13C chemical shifts
of a given compound with those of its derivative.
Structural information can be gained from these signal
displacements. Such derivatization may be realized
either in situ, by adding a given reagent to the sub-
strate solution in the NMR tube, or by a separate
chemical reaction prior to the measurement.
The reaction of hydroxylated compounds and
amines with trichloroacetyl isocyanate (TAI)55to form
urethanes and ureas, r e ~ p e c t i v e l y ,belongs
~~ to the first
category. Figure 8 depicts the TAI-induced shifts for
phenol and aniline.56
58 ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982
+ 5.03 + 5.19
Figure 8. TAI-induced shifts for phenol and aniline.56
This method, however, is restricted to compounds
containing those functionalities, and there is only one
application in the 13C NMR field of coumarin deriva-
t i v e ~ Moreover,
.~~ there is a fall-off in the solubility of
the urethanes and ureas derived from the aromatic
parent compounds.56
Derivatization of the second category implies a
chemical reaction or synthesis which cannot be con-
ducted in the NMR tube. Very valuable derivatives in
this sense are those where one or more hydrogens are
replaced by deuterium at specific positions.57 Thereby,
for example, a methine signal is split into a 1 : l :1
triplet due to one-bond deuterium-carbon coupling
(deuterium spin quantum number I = 1, cf. signal of
deuteriochloroform). Further, its total intensity is de-
creased by less efficient spin-lattice relaxation and
nuclear Overhauser enhancement. Thus, in practice,
the signal of a deuteriated carbon almost disappears in
the spectrum. For adjacent carbons slight line
broadenings ["J(CD), n = 2,3] and isotope shifts of a
few tenths of a ppm have to be e ~ p e c t e d . ~Selective '
deuteriation of coumarins has been used in some
instances. 3-Deuterio- and 4-deuterio-coumarin have
been investigated for signal assignments,'* as well as
3 - d e u t e r i o - 4 - h y d r o x y c o ~ m a r i n ~and
~ ~ ~ ~6,7-dideu-
teri0-4-hydroxycoumarin.~~ In the latter case the C-5
signal was unambiguously identified and distinguished
from that of C-6.36 Selective deuteriation, however, is
depreciated since it is often, synthetically, a laborious
procedure.
It was recently shown that the preparation of
coumarinic t h i o n o l a c t ~ n e s , and ~ ~ ~ comparison
~~ of
their 13CNMR data with those of the parent com-
pounds, is a valuable tool for spectral assignments, at
least for the pyrone ring carbon^.^^.^^
Figure 9a shows the thionolactone formation shifts
for coumarin itself. It emerged46 that the values re-
main practically the same for 7-methoxycoumarin
(herniarin, 34) and psoralen (159), and also for a
number of furanocoumarins substituted on the ben-
zene and furan ring.46 Very similar values had already
been reported earlier for coumarin.62 For 2 - p y r 0 n e ~ ~
and 3,6- and 4,6-diphenyl-2-pyr0ne,~~however, the
corresponding shifts differ remarkably (see Fig. 9b-d),
so that at least for coumarins substituted on the
pyrone ring the rule given in Fig. 9a probably no
longer applies quantitatively; the shift trends,
nevertheless, are expected to persist. Further investi-
gations in this direction are desirable.
Finally, acetylation of hydroxy groups is
recommended-a method64 which has scarcely been
used6' with this family of compounds: the a-carbons
 13CNMR SPECTROSCOPY OF COUMARIN DERIVATIVES
2B(34;
2.3
X
Ph
Figure 9. T hionolactone formation s hifts.46,62,63
experience marked upfield signal shifts, whereas ortho-
and para-carbons are clearly deshielded and meta-
carbons are left more or less unchanged.
13C CHEMICAL SHIFTS AND SUBSTITUENT
EFFECTS OF COUMARIN DERIVATIVES
During the past two decades numerous publications
have appeared calculating 13C chemical shifts by ab
initio and semi-empirical M O and cor-
relating the experimental shielding data with the
physicochemical parameters and structural properties
of the molecules.1~66~6'-70
There have also been attempts to predict the I3C
chemical shifts of coumarins. The first to do so was
S ~ j k awho
, ~ ~found a fairly good correlation between
the carbon shifts of coumarin and its protonated de-
rivative with the 7~ charge densities calculated by the
C N D 0 / 2 method.71 Shortly afterwards, Giinther et
aL2' reported that substituent effects (SCS) in various
mono- and di-methoxycoumarins correlate well with
the HMO atom-atom polarizabilities, mii : 7 2
SCS = K r i j (KOCH3= 80.13) (2)
Although this approach is purely empirical, it seems to
be useful for peak assignments, not only for coumarins
but also for other unsaturated molecule^.^'^^^ Further-
more, Gunther et aL2' also found a result similar to
S ~ j k a ' swhen
~ ~ correlating coumarin shifts with 7~
charge densities calculated by the Hiickel MO
method.73 This, however, fails for methoxylated
coumarins," demonstrating that simple charge
density-shift relationships are not generally applicable
reliably. E r n ~ reported
t ~ ~ a linear relationship between
@-methyl substituent effects in unhindered methylated
coumarins and the 7~ bond order, P,, of the C-a!-C-@
bond calculated by the INDO MO method:71
@ SCS=13.49-19.80 P, (3)
which may be applicable for signal assignment. In a
more rigorous way, Grigor and Webb74 reproduced
the 13C shieldings of coumarins and some mono- and
di-methoxycoumarins by refined INDO MO calcula-
tions and found that, in addition to atom-atom
polarizabilities2' and 7~ bond other factors
such as excitation energies and electron-nucleus dis-
tances ((r-3)2p)1 play an important role in the determi-
nation of the 13C chemical shifts of these compounds.
There are two studies correlating substituent-induced
chemical shifts (SCS) with substituent parameters.
Gottlieb et investigated the SCS on the pyrone
ring carbons C-2, C-3, C-4, C-9 and C-10 in 6- and
7-substituted coumarins, and found good correlations
of the ring-junction atoms C-9 and C-10 with the
Hammett constants and of C-2 and C-4 with (T,
and, separately, with up.Moreover, the correlation of
the C-3 chemical shifts with u+ is excellent. This
behaviour is strongly reminiscent of related data for
substituted s t y r e n e ~ , ~so' that Gottlieb et al. concluded
that the SCS are transmitted essentially via the -
CH=CH-CO- moiety, the lactone group insulating
the alternative transmission pathway.
Rabaron et aL3' described a three-parameter corre-
lation of the 13C chemical shifts of various 3-
substituted 4-hydroxy- and 4-hydroxy-7-
methoxycoumarins with 9,76 %!76 a nd Q77:
SCS = a 9 + b 9 + c Q + d (4)
The use of Swain and Lupton's parameters 9 and 9
alone does not yield satisfactory results.38
Although the aforementioned calculations and cor-
relations are of great merit by allowing deep insight
into charge densities and SCS transmission mechan-
isms, practical applications are hampered by their
inherent restrictions and limitations. Comparisons of
SCS in coumarins with those in related molecular
systems, such as substituted naphthalenes, also give
interesting results which can be used diagnostically. In
the following sections, the SCS of various monosubsti-
tuted coumarins (Table 1) are discussed along these
lines.
a Effects
In general, the aSCS are similar to those of corres-
ponding 1- and 2-substituted naphthalene^.^^^^^^^'-^^
There are only a few exceptions. Mysteriously, the
a -methyl effect in 7-methylcoumarin (31)is consider-
ably larger than for all other isomers ( 1 1 . 2 ~ 8.3-
~.
9.7 ~ p m ) Despite
. ~ ~ the similarity of the a-hydroxy
effects in 4-hydroxycoumarin (13) and 1-naphthol
(22.4 and 23.4 ppm, respectively), the corresponding
methoxy effects are quite different (22.6 and
27.6ppm, respectively). In 6-cyano- (23) and 7-
nitrocoumarin (47) the a! SCS are smaller than in 2-
cyano- and 2-nitronaphthalene by ca. 3 ppm. Again,
there is no satisfactory explanation.
ortho Effects (p)
By analogy with naphthalenes,s2 the @ SCS in couma-
rins depend strongly on the positions of the sub-
stituents and the affected carbons: for 4-, 5-.and
ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982 59
 H. DUDDECK AND M. KAISER

Table 1. Substituent effects (SCS) in various monosubstituted coumarins

Substituent c-2 c-3 c-4 c-5 C-6 c-7 C-8 c-9 c-10

3-CH3 1.7 9.3 -4.4 -1.1 -0.1 -1.4 -0.1 -0.7 0.8
3-COOH -3.2 1.8 4.9 2.2 0.5 2.6 -0.2 0.7 -0.7
3-OH -1.9 25.3 --28.6 -1.8 0.1 -4.3 -0.8 -4.7 1.9
3-CI -3.9 4.4 -2.9 -0.2 0.5 0.0 -0.3 -1.7 0.0
3-Br -4.1 -5.4 0.4 -1.2 0.1 -0.2 -0.4 -1.3 0.0
4-CH3 0.1 -1.3 8.7 -3.5 -0.2 -0.1 0.5 -0.4 1.2
4-OH 2.5 -25.1 22.4 -4.7 -0.9 0.3 -0.3 -0.2 -2.7
4-OCH3 2.1 -26.4 22.6 -5.3 -0.7 0.4 0.1 -0.8 -3.3
5-CH3 0.2 -0.5 -3.2. 8.2 1.3 -0.2 -1.7 0.7 -1.1
6-CH3 0.5 0.1 -0.2 -0.3 9.7 1.o 0.1 -1.7 -0.2
6-CHO 0.3 1.5 0.4 2.9 9.0 0:9 1.9 4.2 0.9
6-COOH 0.8 0.9 0.7 2.6 3.4 1.8 0.9 3.1 0.2
6-CN -0.2 2.3 -0.4 5.2 -15.5 3.6 2.3 2.9 2.1
6-OH -0.3 -0.3 . 0.2 -15.7 29.3 -12.1 0.5 -7.1 0.3
6-OCH3 -0.3 0.7 -1.0 -18.3 31.5 -12.8 1.3 -5.5 0.3
6-OCOCH3 1.3 1.o 0.4 -7.3 22.8 -5.8 1.7 -2.2 1.0
6-NH2 2.4 0.0 1.0 -15.9 20.0 -11.3 1.1 -6.7 0.9
6-N02 -0.4 2.4 -0.2 -3.7 20.2 -4.8 2.0 4.0 0.7
6-CI -0.8 1.2 -1.7 -1.3 5.0 -0.4 1.6 -1.8 0.8
6-Br -1.0 1.I -1.8 1.8 -7.7 2.4 1.9 -1.2 1.4
7-CH3 0.5 -1.0 -0.2 -0.5 1.2 11.3 0.5 0.3 -2.3
7-COOH 1.2 1.6 0.2 0.5 1.5 2.8 2.1 0.0 3.8
7-OH 0.3 -4.9 0.7 1.5 -11.1 29.8 - 13.9 1.8 -7.3
7-OCH3 0.4 -3.7 -0.3 0.6 -12.3 30.8 -15.8 1.7 -6.5
7-OCOCH3 1.3 -0.4 0.6 1.2 -5.4 22.0 -5.7 1.0 -1.6
7-NH2 3.2 -6.8 1.6 1.4 -11.8 20.7 - 15.9 2.7 -8.5
7-NO2 -0.3 3.7 -1.0 1.4 -4.9 16.4 -3.7 0.2 5.3
7-CI 0.6 0.1 0.1 1.2 1.I 6.3 0.9 0.6 -0.9
7-Br -1.0 0.2 -1.2 0.5 3.2 -6.3 3.4 0.2 -1.2
8-CH3 0.5 -0.1 0.2 -2.5 -0.4 1.4 9.9 -1.5 -0.2
8-OH -0.4 -0.3 0.9 -9.7 0.0 -13.4 28.3 -11.5 0.9
8-OCH3 -1.0 0.5 -0.6 -9.1 -0.5 -18.2 30.8 -9.1 0.5

8-substituted coumarins the substituents shield the

neighbouring methine carbons to a greater extent than
the quaternary carbons; for 6- and 7-substituted
coumarins the differences of the p effects are smaller
than in the corresponding naphthalenes. The averages
of the two p SCS for a certain substituent in both
systems, however, are approximately the same, show-
ing that the p SCS reflect a subtle balance of canonical
forms and electric field influences.82 This is demon-
strated in Fig. 10 for 4-hydroxycoumarin (13).
The electron density at C-3 is higher than at C-9,
because the canonical structure 13a is much more
favoured than 13b. The latter does not retain the 7~
electron sextet of the benzene ring8* and, further, it is
tetraionic. The possible a-pyrone-y-pyrone tautomer-
ism,59.83 however, is not involved in this discrepancy
between the coumarinic and naphthalenic system,
since methoxy derivatives reveal similar effects.
Abnormal p effects exist for substituents in the
3-position. This can be interpreted in terms of in-
tramolecular interactions (electronic, steric and/or by
hydrogen bridging) between the substituents and the
neighbouring carbonyl group. Such interaction effects
are discussed below.
It has already been noted that P-methyl effects at
ortho carbons can be correlated to 7~ bond orders.34
Substituent effects at meta positioned carbons are
small, in agreement with those of naphthalene deriva-
tives. Methyl and carboxyl SCS are negligible, whereas
those of hetero substituents are generally downfield
(up to 2.5 ppm).
This type of molecular arrangement, which leads to
the well known (‘steric’) diamagnetic y SCS,’,82,84is
represented only in a few cases among the available
data for monosubstituted coumarins: 4-X * * . C-5 (X =
CH3, OH, OCH,) and 5-CH3 * * * C-4. As expected,
the SCS values are -3.2 to -5.3 ppm.
Additionally, some ysynSCS can be estimated from
the spectra of some di- and tri-substituted coumarins.
The effect of the 4-phenyl group on C-5 in 4-phenyl-
7-hydroxycoumarin (84), when compared with 7-
hydroxycoumarin (33), is only -1.5 to -2.0 ppm if
intramolecular interaction is permissibly neglected.
The low value may be a consequence of the anisotropy
of the phenyl group; this, however, is not observed in
aliphatic molecules such as 2 - p h e n ~ l a d a m a n t a n e . ~ ~

60 ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982

 I3C NMR SPECTROSCOPY OF COUMARIN DERIVATIVES

OH

0
&J OH

\ -17.0

Figure 12. Canonical form of umbelliferone (33).

@ A similar value is observed by comparing the C-3

@OH OH chemical shifts of 4-methylumbelliferone (80, 6 =
110.4)33 and 4-methylcoumarin (12,S = 115.1).34 An
analogous comparison of 6(C-3) of 8329and 1234gives
an SCS of -7.1 ppm for the diethylamino substituent,
which is an even stronger electron-donating function
e than a hydroxy
Other long-range SCS are small, or even negligible,
130 13b within the limit of experimental error and reproduci-
bility.
Figure 10. p SCS in 4-hydroxycoumarin (13) and 1-naphth01.7~

EFFECTS OF INTRAMOLECULAR INTER-

ACTION ON SUBSTITUENT EFFECTS

Likewise, a 5-methoxyl ysyn SCS of -5 to -6ppm at
C-4 may be deduced from the data for 91,94and 125.
para Effects (ti)
As has been shown by Ernst79-82 for naphthalene
derivatives, para SCS can amount up to *lo ppm, and
can be correlated linearly with total charge density
changes calculated by INDO MO methods. This also
seems to hold for 6- and 7-substituted coumarins,
because fairly good correlations exist between respec-
tive para effects in both molecular systems. Exceptions
only occur for 3-carboxycoumarin (8) and 3-hydroxy-
coumarin (9),which are probably due to intramolecu-
lar hydrogen bridging. Analogous observations are
noted in connection with ortho effects.
It is a well known and often reported fact that indi-
vidual SCS in molecules with more than one sub-
stituent are additive, unless there is an intramolecular
interaction between them. This is also mentioned in a
number of I3C NMR studies on coumarinic com-
p o u n d ~ . ~ ~ A ,systematic
~ ~ ~ ~ investigation
~ , ~ ~ , ~ of~ the
data in this review confirms these findings (see Table
2).
Non-additivity (NA) effects occur only when func-
tional groups within the molecule interact electroni-
cally, sterically, by hydrogen bridging or by other
mechanisms. One case has already been discussed in
the previous section-the effects of substituents in the
3-position are altered by the influence of the neigh-
bouring lactone group. On the whole, one has to allow
for NA effects if the substituents are in close
proximity.

Substituents at vicinal carbon atoms

Long-range effects
The C-3 signals of 3-chloro- and 3-bromo-4-
Long-range effects differ in some cases from those of hydroxycoumarins (63,114 and 64) appear at lower,
naphthalenes, as demonstrated in Fig. 11. and those of C-4 at higher, field than expected by
Apparently, in 6-substituted coumarins the effects assuming additivity. In methylhydroxy derivatives 53,
cannot be transmitted to the carbonyl group, since the 109 and 123 only the hydroxylated carbons are
corresponding canonical form is highly unfavoured. affected; and only slight deviations from additivity, if
On. the other hand, in umbelliferone (33) the at all, are observed for dimethyl (89,95and 121)and
mesomeric structure (Fig. 12) is of exceptional impor- dihydroxy derivatives (97,104, 122 and 124).Appar-
tance. ently, these interaction effects are mainly of electronic
rather than steric origin. In dimethoxy compounds 100
and 107, however, clear NA effects are observed at
the substituted and the neighbouring unsubstituted
carbons. The finding that the methine signals in the a
position to methoxylated carbons (C-5/C-8 in 100 and
C-6 in 107)feature negative NA effects, suggests that
X=COOH +2.5 + 0.8 + 1.6
the conformational behaviour of the methoxy groups
X=OH - 2.1 -0.3 -4.9
is sterically perturbed. The methyl groups are forced
Figure 11. Long-range SCS in naphthalenes3482compared with outwards, increasing their diamagnetic ysyneffects (see
coumarins. Fig. 13).

ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982 61

 H. DUDDECK AND M. KAISER

Table 2. Non-additivity effects (a,,, - 6ralr)ain di- and tri-substituted coumarins

Substituents c-2 c-3 c-4 c-5 C-6 c-7 C-8 c-9 c-10

3-CH3.4-OH -1.4 -0.1 -1.9 0.8 0.3 0.6 0.0 -1.2 -0.5
3-COOR, 4-OH -3.1 1.2 1.1 -1.1 0.5 0.8 0.6 -0.7 -1.1
3-CI, 4-OH -0.4 3.2 -2.6 0.3 0.4 0.4 0.5 -0.8 -0.1
3-Br, 4-OH -0.3 3.5 -4.1 1.3 0.6 0.8 0.6 -0.7 0.2
3-Br, 6-Br 0.4 -0.1 1.3 0.9 0.6 0.2 0.3 0.2 -0.4
4-CH3, 6-OH -0.3 -0.4 1.2 0.5 -1.2 0.1 -0.3 -0.1 -0.2
4-CH3.7-CH3 0.4 0.1 0.6 0.4 0.2 0.2 0.0 0.1 0.1
4-CH3.7-OH -0.4 0.2 0.2 0.1 -0.2 -0.3 -0.6 -0.3 -0.5
4-OH, 7-OCH3 -0.9 1.1 0.4 0.4 0.5 0.2 0.3 0.2 -0.4
4-OCH3,7-OCH3 -0.3 1.o 0.3 0.2 0.2 -0.4 -0.6 -0.3 -0.5
5-CH3, 6-CH3 0.0 0.0 0.7 -1.8 -2.6 1.1 -0.5 1.9 -b

5-CH3, 7-OCH3 -0.5 -0.4 -0.3 -0.2 0.0 -0.7 -0.5 1.0 -0.1
5-CH3, 8-CH3 -0.4 -0.7 -0.8 -1.0 -0.9 -1.0 -1.8 0.3 -1.0
6-CH3, 7-CH3 0.2 0.2 0.4 0.9 -1.9 -1.9 0.6 0.3 0.6
6-OH, 7-OH 1.o 0.8 0.4 -1.0 0.6 1.1 0.2 0.5 -0.4
6-OCH3, 7-OCH3 0.2 0.1 0.5 -2.4 2.6 3.0 -2.0 -0.1 -1.4
6-CH3,8-CH3 -1.6 -1.4 -0.8 -0.7 -1.1 -0.9 -1.8 -1.1 -1.0
7-OH, 8-OH 0.8 0.5 0.2 -0.5 -0.3 1.8 1.8 0.0 0.3
7-OCH3, 8-OCH3 -0.1 0.3 0.4 2.8 -3.3 11.0 4.9 1.6 0.9
3-CH3,4-OH, 7-OCH3 -1.2 0.8 -0.9 1.3 0.4 0.5 0.0 -1.2 0.9
3-CI, 4-OH, 7-OCH3 0.3 4.4 -2.1 0.9 0.6 0.0 0.6 -0.7 -0.5
4-OCH3, 5-CH3, 7-OCH3 -0.4 1.6 6.6 6.6 2.7 -1.2 -0.4 0.8 -0.3
4-OCH3, 5-CH3, 8-OCH3 0.1 0.2 6.8 5.6 1.9 -0.3 -0.1 -0.2 0.0
4-CH3,6-CH3,7-CH3 0.0 0.0 0.7 1.2 -2.0 -2.1 0.3 0.1 0.4
4-CH3,6-OH, 7-OH 0.3 0.7 -0.2 -0.8 0.4 0.8 -0.6 -0.2 -1.1
4-CH3,7-OH, 8-CH3 -0.5 0.0 -0.1 -1.1 -0.9 -3.8 -2.9 -0.7 -0.3
4-CH3,7-OH, 8-OH 0.3 0.6 2.0 -0.7 -0.5 1.5 1.2 0.1 -0.3
a aeexp,experimental chemical shift; Scat,, chemical shift calculated assuming additivity of individual SCS.
Experimental value not reported.

Cti3*-., Highly substituted coumarins

It stands to reason that with an increase in the number

of substituents attached to the basic coumarin mole-
cule there is an increase in the Na effects, and these
become increasingly unpredictable. For example, the
individual SCS of a given group in, for example, a fur-
anocoumarin may be quite different from that in couma-
rin itself or in benzene. Thus, spectral interpretations
which are based solely upon such SCS comparisons
should be regarded with caution. Indeed, misassign-
Figure 13. Steric perturbation of methoxyl groups.
ments by neglecting this fact have appeared in the
literature, and Fig. 14 demonstrates such different
8-methoxy SCS6' values.
Substituents in peri position

This molecular arrangement is present in coumarins

To
with substituents simultaneously in the 4- and 5 - - 0.5 0
positions. Non-additivity effects can only be evaluated -18.2 \
for two derivatives (119 and 120) bearing 4-methoxy 32.8 30.8
and 5-methyl groups. They are distinctly positive at
the substituted carbons' signals (+5.6-+6.8 ppm), and OCH, &CH3
the neighbouring atoms C-3 and C-6 are also affected, -8.9
whereas the individual SCS are additive for the
quaternary carbons C-9 and C-10. The magnitudes
and signs of NA effects at these six atoms, however,
seem to be strongly dependent on the nature of the 30.2
substituents. This can be guessed by inspecting
OCH,
dimethyl-,88,89 diamino-*' and dihalo-naphthalene.8*
The origin is apparently severe steric substituent in- Figure 14. Methoxy SCS in psoralen (159), coumarin (1) and
teraction and molecular distorti~n.~' benzene.

62 ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982

 I3C NMR SPECTROSCOPY O F COUMARIN DERIVATIVES

Br Br In order to avoid excessive data, these were re-

-1.0 I to different families of coumarin derivatives, each
R starting with the parent compound if its spectrum is
Figure 15. Brorno SCS in benzene and imperatorin (171).
This is even more drastic for bromo substituents6'
(see Fig. 15). Comparing the 13C chemical shifts of
imperatorin (171) and its tribromo derivative (177),
one obtains 5-bromo SCS which, in part, differ enorm-
ously from those of bromobenzene;' the a! effect, for
example, is 20 ppm smaller.
LIST OF 13C CHEMICAL SHIFI'S
stricted to the carbon atoms of the coumarin and
furano- and pyrano-coumarin nuclei only. The chemi-
cal shifts of all other carbon atoms can be taken from
the original papers, or requested from the authors.
The numbering is uniform.
Table 3 is divided into several sub-tables, according
reported. The entries are grouped according to their
substitution patterns and not to the substituents'
priorities." Thus, a 3-substituted coumarin has a
higher rank than a 4-substituted coumarin, whatever
the substituent. This arrangement facilitates the trac-
ing of derivatives with a given substitution pattern.
In the second column the compounds' designations
are given, together with their trivial names in parenth-
eses if available. Where the designations are too
clumsy, the reader is referred to the molecular for-
mulae in Scheme 1.
The solvents are noted in addition to the data sets.
If there was a choice, the chemical shifts obtained in
CDCI, solution were preferred. For a given entry,
however, each reference containing data for the par-
ticular compound is quoted in the last column.

The 13C chemical shifts of all coumarin derivatives
which were available from the literature (until the end
of 1981), and our own measurements, are listed in
Table 3 and in Scheme 1.
Acknowledgements
The authors are grateful to Frau Elsa Sauerbier for her skilful
assistance in preparing the manuscript. This work was supported by
the Fonds der Chemischen Industrie.

Table 3. 13C chemical shifts of coumarin derivatives'

Monosubstitutedcournarins
No. Name C-2 C-3 C-4 C-5 C-6 c-7 c-8 c-9 C-10 Solvent References

1 Coumarin (see Scheme 1) 160.4 116.4 143.6 128.1 124.4 131.8 116.4 153.9 118.8 CDCI, 4, 28, 29, 31,
34-37,40, 46,
58, 62, 63, 86,
92-95
2 3-Deuterio- 158.6 -b 142.4 127.6 123.8 131.2 116.4 154.0 118.7 CCI4 58
3 4-Deuterio- 158.5 116.3 142.5 127.7 123.9 131.2 116.4 153.9 118.6 CCli 58
4 1-Thio- 185.4 126.0' 143.7 130.0 124.2 131.6 126.5' 137.7 126.2 CDCI, 62
5 2-Thiono- 198.0 129.7 134.5 127.8 125.5 132.2 116.8 156.7 120.5 CDCI, 46, 62, 63
6 1-Thio-2-thiono- 209.0 136.0 131.4 130.3 123.4 134.4 127.7 140.3 128.0 CDCI, 46,63
7 3-Methyl- 162.1 125.7 139.2 127.0 124.3 130.4 116.3 153.2 119.6 CDC13 32,34
8 3-Carboxy- 157.2 118.2 148.5 130.3 124.9 134.4 116.2 154.6 118.1 DMSO-d6 35,96
9 3-Hydroxy- 158.5 141.8 115.0 126.3 124.5 127.5 115.6 149.2 120.7 DMSO 33
10 3-Chloro- 156.5 120.8 140.7 127.9 124.9 131.8 116.1 152.2 118.8 cDci' 97
DMSO-d,
11 3-BrOmO- 156.3 111.0 144.0 126.9 124.5 131.6 116.0 152.6 118.8 CDCI, 31
12 4-Methyl- 160.5 115.1 152.3 124.6 124.2 131.7 116.9 153.5 120.0 CDCI, 32,34
13 4-Hydroxy- 162.9 91.3 160.0 123.3 123.5 132.1 116.1 153.7 116.1 CDCI, 29, 33, 36, 38,
83,98
14 3-Deuterio-4-deuterioxy- 163.6 91.9 167.9 124.6 125.2 133.9 117.6 155.2 117.6 CD,OD 59
15 4-Oxide-anion 166.6 87.1 177.2 -b -b - b - 161.6 104.7 DMSO-d6 99
16 4-Methoxy- 162.5 90.0 166.2 122.8 123.7 132.2 116.5 153.1 115.5 CDCI, 33, 36, 87
17 4-Allyloxy- 162.5 90.8 164.9 122.8 123.7 130.5 116.5 153.2 115.5 CDCI, 100
18 4-lsopentenyloxy- 160.5 90.8 164.4 123.0 123.6 132.1 116.6 151.5 115.9 CDCI, 100
19 5-Methyl- 160.6 115.9 140.4 136.3 125.7 131.6 114.7 154.6 117.7 CDCI, 34,101
20 6-Methyl- 160.9 116.5 143.4 127.8 134.1 132.8 116.5 152.2 118.6 CDCI, 32, 34, 40, 86
19,7 CDCI,+CHoOH
21 6-Carbaldehyde 160.7 117.9 144.0 131.0 133.4 132.7 118.3 158.1 40
(2:l)
22 6-Carboxy- 161.2 117.3 144.3 130.7 127.8 CDCI,+CH,OH
133.6 117.3 157.0 119.0 40
(2:l)
23 6-Cyano- 160.2 118.7 143.2 133.3 108.9 120,9 CDCI,+CH,OH
135.4 118.7 156.9 40
(2:l)

ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982 63

 H. DUDDECK AND M. KAISER

Table 3. (Continued).
No. Name C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 Solvent References

24 6-Hydroxy- 160.1 116.1 143.8 112.4 153.7 119.7 116.9 146.8 119.1 DMSO 33,40
CCI4+ CDCI, 28,40
25 6-Methoxy- 160.1 117.1' 142.6 109.8 155.9 119.0" 117.7' 148.4 119.1
(3 : 2)
26 6-Acetoxv 161.7 117.4 144.0 120.8 147.2 126.0 118.1 151.7 119.8
+
CDCI, CH,OH 40
(2:l)
CDCI, + CH30H 40
27 6-Amino- 162.8 116.4 144.6 112.2 144.4 120.5 117.5 147.2 119.7
(2:l)
28 6-Nitro- 160.0 118.8 143.4 124.4 144.6 127.0 118.4 157.9 119.5
+
CDC13 CH,OH
40
(2:1)
29 6-Chloro- 159.6 117.6 141.9 126.8 129.4 131.4 118.0 152.1 119.6 CHCI, 29,40
30 6-Bromo- 159.4 117.5 141.8 129.9 116.7 134.2 118.3 152.7 120.2 CDCI, 31
31 7-Methyl- 160.9 115.4 143.4 127.6 125.6 143.1 116.9 154.2 116.5 CDCI, 32,34, 40,
101
CDCI, + CH,OH 40
32 7-Carboxy- 161.6 118.0 143.8 128.6 126.0 134.6 118.5 154.0 122.6
(2:1)
33 7-Hydroxy-(umbelliferone) 160.7 111.5 144.3 129.6 113.3 161.6 102.5 155.7 111.5 DMSO 29, 33, 35,40,
95
34 7-Methoxy4herniarin) 160.8 112.7 143.3 128.7 112.1 162.6 100.6 155.6 112.3 CDCI, 28, 32, 37,40,
86,58
162.7 112.7 CDCI, + CH@H 40
35 7-Ethoxy- 144.8 129.4 113.6 162.8 101.6 156.1 112.9
(2:l)
36 7-Allyloxy- 160.4 112.4' 142.9 128.4 112.5' 161.2 101.2 155.2 112.1 CDCI, 93
37 7-lsopentenyloxy- 160.1 111.9 142.7 128.1 112.1 161.2 100.6 154.9 111.6 CDCI, 35
38 7-Epoxyisopentenyloxy- 160.8' 112.7 143.2 128.9 113.1 161.7' 101.7 155.7 112.9 CDCI:, 103
39 7-Geranyloxy4aurapten) 160.7 112.5' 143.0 128.3 112.7' 161.7 101.3 155.4 112.1 CDCI, 39,93,102
40 Marmin (see Scheme 1) 160.1 112.2 144.0 129.2 112.7 161.5 101.3 155.2 112.2 DMSO-d6 93
41 Colladonin (see Scheme 1) 161.O 112.6 143.3 128.6 112.6 162.0 101.2 155.6 112.3 CHCI, 4
42 Colladin (see Scheme 1) 160.7 112.6' 143.0 128.4 112.7' 161.7 101.0' 155.5 112.1 CDCI, 4
43 7-~~-glucosyl-(skimmin) 160.3 113.2 144.2 129.5 113.8 160.3 103.4 155.1 113.4 DMSO 33
44 7-Acetoxy- 161.7 116.0 144.2 129.3 119.1 153.8 110.7 154.9 117.2
+
CDC13 CH3OH
40
(2:l)
45 7-Phenylacetoxy- 160.2 116.7 142.8 128.6 118.3 154.7 110.3 153.3 116.1 CDClj 94
46 7-Amino- 163.6 109.6 145.2 129.5 112.6 152.5 100.5 156.6 110.3
+
CDC13 CH,OH
40
(2:l)
CDC13 + CH,OH
47 7-Nitro 160.1 120.1 142.7 129.5 119.5 148.2 112.7 154.1 124.1 40
(2:l)
7-Chloro- 161.0 116.5 143.8 129.3 125.5 117.3 CDC13+CH30H 40
40 138.1 154.5 117.9
(2:l)
49 7-BrOmO- 159.4 116.6 142.4 128.6 127.6 125.5 119.8 154.1 117.6 CDCI, 31
50 8-Methyl- 160.9 116.3 143.8 125.6 124.0 133.2 126.3 152.4 118.6 CDC13 32,34
51 8-Hydroxy- 160.0 116.1 144.5 118.4 124.4 118.4 144.7 142.4 119.7 DMSO 33
159.4 143.0 CCI,+ CDCI,
52 8-Methoxy- 116.9 119.0 123.9 113.6 147.2 144.8 119.3 28
(3:2)

Disubstituted coumarins
53 3-Methyl-4-h ydroxy- 163.2 100.5 159.7 123.0 123.7 131.3 116.0 151.8 116.4 DMSO-d6 38,83
54 3-Benzyl-4-hydroxy- 162.9 104.4 160.6 123.3 123.7 131.6 116.1 152.1 116.3 DMSO-d6 38,83
55 (See Scheme 1) 159.6 110.2 164.5 122.4 123.3 131.7 116.6 154.5 112.6 CDCI, 100
56 Phenprocoumon (see Scheme 1) 161.6 107.9 160.7 123.4 123.7 131.7 116.3 152.2 116.1 DMSO-d6 36,104
57 Warfarin methyl ether (see Scheme 1) 162.3 119.8 164.2 126.7 123.5 131.4 116.6 153.0 116.8 CDCI, 36
58 Sodium warfarin (see Scheme 1) 167.9 103.4 175.7 126.6 123.9 131.6 116.7 153.5 122.3 Dioxane 36,104
59 3-Acetyl-4-h ydroxy 159.9 101.4 177.8 124.7 125.1 136.6 116.8 154.1 114.7 DMSO-d6 38
60 3-Ethoxycarbonyl-4-hydroxy- 156.6 94.3 172.0 124.4 124.5 135.5 116.5 153.7 114.3 DMSO-d6 38
61 3-Phenyl-Qhydroxy- 161.9 106.2 160.3 123.8 123.8 132.1 116.1 152.3 116.5 DMSO-d6 38,83
62 3-Phenoxy-4-hydroxy- 158.4 119.9 155.4 123.5 124.3 131.7 116.2 150.9 116.5 DMSO-d6 38
63 3-Chloro-4-hydroxy- 158.6 98.9 160.5 123.4 124.4 132.5 116.3 151.2 116.0 DMSO-d6 38
64 3-Bromo-4-hydroxy- 158.5 89.4 162.3 123.4 124.2 132.7 116.3 151.7 116.3 DMSO-d6 36,38
65 3-Nitro-4-hydroxy- 156.1 121.2 163.9 124.3 125.6 134.2 116.6 152.4 117.8 DMSO-d6 38
66 (See Scheme 1) 159.8 106.8 177.0 -b -b -b - 154.1 118.3 DMSO-d6 99
67 (See Scheme 1) 160.2 107.3 177.1 -b -b -b - 154.3 118.6 DMSO-d6 99
68 (See Scheme 1) 159.9 107.2 177.1 -b -b -b - 154.1 118.2 DMSO-d, 99
69 (See Scheme 1) 158.3 106.9 176.9 -b -b -b - 154.0 118.6 DMSO-d8 99
70 (See Scheme 1) 156.8 107.8 176.8 -b -b -b - 154.1 118.4 DMSO-d6 99
71 (See Scheme 1) 159.4 109.2 177.1 -b - b -b - 153.2 118.3 DMSO-d6 99
72 3.6-Dibromo- 155.7 112.0 143.5 129.6 120.9 134.2 118.2 151.6 116.3 DMSO 31
73 3-(1,l '-Dimethylallyl)-7-methoxy- 159.9 131.7 137.6 128.5 112.2 162.0 100.0 154.9 112.9 CDCI:, 102
74 3-Phenyl-7-methoxy- 160.5 124.7 139.8 128.7 112.6 162.5 100.3 155.2 113.2 CDCI, 65
75 3.8-Dimethyl-1 -thio-Z-thiono- 208.7 141.0' 130.5 129.0 126.9 135.0 131.3 140.8' 129.3 CDCI, 62
76 Dibenzothiopyran-Zone (see 186.2 127.0 132.2 -b -b - b - 136.0 128.5 CDCl, 62
Scheme 1)
77 Dibenzothiopyran-2-thione 212.5 134.6 130.2 -b -b - b - 127.9 135.0 CDCI, 62
78 4-Methyl-6-hydroxy- 159.9 114.4 i53.7 109.4 152.3 119.7 117.1 146.3 120.1 DMSO-d6 95
79 4.7-Dimethyl- 161.4 114.2 152.7 124.5 125.6 143.2 117.4 153.9 117.8 CDC13 101
80 4-Methyl-7-hydroxy- 160.4 110.4 153.2 126.2 112.9 161.2 102.4 155.0 112.2 DMSO 29,33

64 ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982

 13CNMR SPECTROSCOPY OF COUMARIN DERIVATIVES

Table 3. (Continued).
No. Name c-2 c-3 c-4 c-5 C-6 c-7 c-8 c-9 c-lo Solvent Reference
81 4-Methyl-7-a-o-glucosyl- 160.0 111.7 153.3 126.3 113.9 160.0 103.8 154.4 -b DMSO 33
82 4-Methyl-7-~o-glucosyl- 160.3 111.9 153.4 126.4 113.6 160.3 103.5 154.5 114.3 DMSO 33
83 4-Methyl-7-diethylamino- 161.6 108.0 152.5 125.0 108.0 150.1 97.1 155.5 108.4 CDCI, 29,105
84 4-Phenyl-7-hydroxy- 160.3 110.4 155.8 127.9 113.1 161.6 102.9 155.4 110.8 +
CDC13 DMSO-d6
65,106
(3:7)
85 4-Phenyl-7-methoxy- 160.9 111.7 155.8 127.8 112.1 162.6 101.0 155.6 112.4 CDC13 65
86 4-Phenyl-7-acetoxy- 160.1 110.5 156.0 127.7 117.9 153.0 114.3 154.6 116.6 CDCl3 65
87 4-Hydroxy-7-methoxy- 162.4 88.7 166.1 124.4 111.7 163.1 100.6 155.6 109.2 DMSO-d6 38
88 4.7-Dimethoxy- 162.6 87.3 166.2 123.6 111.6 162.6 100.1 154.5 108.5 CDC13 86
89 5,g-Dimethyl- 161.1 116.0 140.9 134.2 132.8 133.7 114.3 153.4 -b CDCI, 101
90 5-Methyl-7-methoxy- 160.5 111.8 139.8 136.7 113.4 161.7 98.4 155.9 111.1 CDC13 86
91 5,7-Dimethoxy-(citropten, timettin) 156.7 103.7 138.1 160.6' 94.6" 163.5' 92.7' 156.7 110.9 +
CCl4 CDClj
28.95
(3 :2)
92 5-Geranyloxy-7-methoxy- 161.3 110.4 138.7 156.0 95.5 163.5 92.5 156.5 104.0 CDCI, 35
93 5,8-Dimethyl- 159.7 114.5 139.8 132.8 124.4 132.0 122.8 152.0 116.5 CDCl3 32
94 5.8-Dimethoxy- 159.4 114.7' 138.2 149.5 103.7 114.9' 141.3' 144.7' 110.2 CCI4+ CDCI,
28
(3:2)
95 6,7-Dimethyl- 161.6 115.7 143.6 128.2 133.4 142.2 117.6 152.8 116.9 CDC13 101
96 6-Geranyl-7-hydroxy-(ostruthin) 162.9 111.2 144.6 127.8 126.4 158.9 102.7 153.8 111.8 CDCI, 39
97 6,7-Dihydroxy-(esculetin) 161.4 112.0 144.5 112.9 143.2 150.6 103.2 149.1 111.4 DMSO 33, 35, 95
98 Diospyroside (see Scheme 1) 160.6 .112.7 144.0 113.4 143.4 148.6 103.2 147.7 113.0 DMSO 107
99 6-~o-Glucosyl-7-hydroxy-(esculin) 160.5 112.1 144.4 115.0 142.6 151.4 103.1 150.5 110.8 DMSO-d6 4, 33,95
160.7 113.5 142.8 108.0 146.2 152.8 99.9 150.0 111.2 CCli + CDC13
100 6,7-Dimethoxy-(scoparon, scoparin) 28,95
(3:2)
101 6.8-Dimethyl- 159.8 115.0 142.8 124.6 132.6 133.3 124.6 . 149.6 117.4 CDCI, 32
102 6-Ethyl-8-methyl- 161.3 116.2 143.9 124.2 140.0 133.3 126.0 150.7 118.5 CDC13 34
103 7-Methoxy-8-isopentenyl-(osthol) 160.9 112.4 143.5 126.0 107.1 159.9 117.4 152.4 112.6 CDC13 4, 35,39
104 7,8-Dihydroxy-(daphnetin) 161.1 111.7 145.4 119.4 113.0 150.0 132.6 144.2 112.7 DMSO 33
105 7-Hydroxy-8-~~-glucosyl- 160.1 113.4 144.7 118.3 114.5 148.2 134.0 144.7 112.3 DMSO-d, 95
106 7-~~-Glucosyl-8-hydroxy-(daphnin) 160.1 113.5 144.8 124.2 111.7 153.4 131.4 144.8 112.3 DMSO-d6 95
107 7.8-Dimethoxy- 159.7 113.5' 143.1 122.4 108.3' 155.4 136.3 148.1 113.7 +
CC14 CDC13
28
(3 : 2)
108 Naphthothiopyranthione (see 206.4 136.6 131.3 - b -b - b - b
141.9 130.9 CDClj 62
Scheme 1)

Coumarins with more than two substituents

109 3-Methyl-4-hydroxy-7-methoxy- 163.8 97.7 160.4 124.1 111.5 162.0 100.2 153.5 109.7 DMSO-d6 38
110 3-Benzyl-4,5-dihydroxy- 162.5 102.4 162.6 154.6 110.2 132.1 107.9 153.1 103.8 DMSO-d6 36
111 3-Benzyl-4-hydroxy-7-methoxy- 163.3 101.8 160.9 124.5 111.6 162.3 100.5 153.9 109.5 DMSO-de 38
112 3-Phenyl-4-hydroxyJ-methoxy- 162.2 103.7 160.6 124.9 111.7 162.7 100.4 154.2 109.6 DMSO-d6 38
113 3-Phenoxy-4-hydroxy-7-rnethoxy- 159.0 118.3 156.2 124.8 112.4 162.5 100.7 152.9 109.6 DMSO-d6 38
114 3-Chloro-4-hydroxy-7-methoxy- 158.9 96.4 160.7 124.6 112.3 162.9 100.6 153.0 109.1 DMSO-d6 38
115 341 ',1 '-Dimethylallyt)-6-isopentenyl- 160.2 131.5 137.9 127.3 127.1 159.9 97.8 153.6 112.3 CDC13 102
7-methoxy-(gravelliferone methyl
ether)
116 3-(1',1 '-Dimethylallyl)-6,7-dimethoxy 160.1 132.3 137.3 108.3 146.3 149.2 99.5 152.2 111.8 CDC13 102
(rutacultin)
117 3-(1',1 '-Dimethylallyl)-7,8-dimethoxy 158.8 131.6 137.6 122.6 108.4 146.6 135.1 154.2 113.7 CDCl3 108
118 3,6,8-Tribromo- 154.9 112.8 143.1 129.2 121.6 136.2 116.4 148.4 109.9 DMSO 31
119 4,7-Dimethoxy-5-methyl-(siderin) 162.7" 87.4 169.3 138.2 115.4 161.6' 98.6 156.3 107.6 CDC13 86
120 4.8-Dimethoxy-5-rnethyC 161.8 90.2 169.2 127.5 126.4 113.5 145.7 144.5 114.9 CDC13 87
121 4,6,7-Trimethyl- 161.6 114.2 152.6 125.0 133.1 141.9 117.8 152.2 117.9 CDC13 101
122 4-Methyl-6.7-dihydroxy- 160.8 110.6 153.0 109.6 142.8 150.2 102.9 148.0 111.9 DMSO 33
123 4,8-DimethylJ-hydroxy- 160.8 110.1 153.1 122.5 111.8 159.1 111.1 153.1 112.0 CDC13 109
124 4-Methyl-7,8-dihydroxy- 160.7 110.5 154.1 115.7 112.6 149.6 132.5 143.6 113.3 DMSO 33
125 Sibiricin (see Scheme 1) 161.1 110.5 138.6 155.7 90.2 161.2 106.0 153.9 103.5 CDC13 35
126 (See Scheme 1) 160.0 114.8 150.3 152.6 105.7 142.2 108.3 155.6 112.4 CDC13 110
127 (See Scheme 1) 161.0 113.0 149.5 152.5 106.2 147.4 107.4 155.8 112.0 CDC13 110
128 3,4,8-Trimethoxy-5-methyl- 159.4 130.5 157.6 127.3 126.9 112.0 145.5 141.0 116.9 CDClj 87
129 4,8-Dimethyl-6-allyl-7-acetoxy- 160.6 114.3 152.3 122.8 119.7 150.4 117.9 151.1 128.5 CDCl3 111
130 Neomammein (see Scheme 1) 159.4 110.1 159.0 158.8 102.3 156.1 104.2 165.4 109.9 CDClj 112,113
131 Mammein (see Scheme 1) 159.4 110.1 159.0 158.8 102.3 156.3 104.5 165.4 109.9 CDC13 112, 114
132 (See Scheme 1) 159.4 112.7 163.2' 154.5' 100.9 156.9' 109.3 159.2 103.1 -b 115
133 (See Scheme 1) 159.4 112.7 154.5' 156.7' 100.9 163.2" 107.3 159.2 108.1 CDC13 112,116

Dicoumarolsd
134 Dicoumarol (melitoxin; see 166.1 102.7 169.8 124.6 124.9 132.4 116.8 153.3 120.2 DMSO-d, 83
Scheme 1)
135 1'-Methyl- 168'8 106.8 164.1 124.0 124.6 132.4 116.4 152.1 117.0 CDC13 98
167.3
169.1 105.8 164.8 124,1 124,6 132,4 116,4 152.3 117.1
136 1'-Ethyl- CDC13 98
167.3 105.5 164.1 152.0 116.4

ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982 65

 H. DUDDECK AND M. KAISER
~~ ~

Table 3. (Continued).
No. Name c-2 c-3 c-4 C-5 C-6 c-7 C-8 C-9 C-10 Solvent Reference

i;,!:: ii:::
169.0 105.9 164.5 124'0 124.6 132.3 116.3
137 1'-n-Propyl- CDC13 98
167.3 105.7 164.1 123.9
169.0 106.0 164.5 116,4 152.2 117.1
138 l'-n-Butyl- 124'0 124.6 132.3 CDC13 98
167.2 105.8 164.0 123.9 152.0 116.4

139 1'-(Z-methyIthioethyl)-
168.8
167.5
105.1 164'9
164.2
123.9 124.7 132.5 116.4 152.2 iii:: CDC13 98

168.8 116,3 152.1 117.0

140 l'-Benzyl. 105.4 164'7 124'0 124.6 132.4 CDC13 98
167.5 164.2 123.9 151.9 116.1
141 1'-Methoxymethyl- 168.2 104.0 164.7 124.0 124.7 132.6 116.4 152.1 116.6 CDC13 98
142 1'-Ethoxycarbonyl- 165.3 103.4 165.7 125.0 124.9 133.3 117.3 153.3 118.4 DMSO-d, 83
169.1 105.5 165.3
143 1'-Phenyl- 124.3 124.8 132.8 116.5 152.3 116.5 CDC13 98
166.9 104.0 164.5
169.1 105.2 165.9
144 1'-(pChloropheny1)- 124.4 124.9 132.7 116.6 152.3 116.6 CDC13 9a
166.7 103.7 164.5
168.9 104.7 166.2
145 1'-(p-Nitrophenyll- 123.8 124.4 133.3 116.7 152.4 116.7 CDC13 98
167.0 103.3 164.7
168.6
146 1'-(o-Chloropheny1)- '05" 164.7 124.3 124.8 132.8 116.5 152.2 116.5 CDC13 98
168.2 104.8
167.9
147 1'-Propionyloxy- 102.3 164.6 124.2 124.7 132.8 116.4 152.0 116.2 CDClj 98
167.8

3.4-Dihydrocoumarins

148 3,4-Dihydrocoumarin 168.5 29.1 23.6 128.1 124.4 128.1 116.8 152.0 122.8 CDC13 96, 112
149 cis-3-Phenyl-4-ethyl- 168.5 49.8 43.9 128.3' 124.0 128.3' 116.8 151.0 127.4' CHC13 117
150 trans-3-Phenyl-4-ethyl- 168.4 50.4 43.9 128.8' 124.6 128.8' 116.6 150.8 127.4' CHC13 117
151 cis-3-Phenyl-4-isopropyl- 169.3 48.9 48.9 129.8' 123.8 128.5' 116.8 152.0 123.8 CHC13 117
152 trans-3-Phenyl-4-isopropyl- 168.6 49.8 48.2 130.1' 124.5 128.4' 116.3 151.1 123.2 CHC13 117
153 cis-3-Phenyl-4-tert-butyl- 169.3 47.8 54.1 130.2' 123.4 128.4' 117.1 151.2 127.4 CHC13 117
154 trans-3-Phenyl-4-tert-butyl- 169.5 46.7 54.4 131.7' 124.0 128.7' 116.6 151.6 121.6 CHC13 117
155 cis-3-Phenyl-4-benzyI- 168.2 49.9 44.4 128.2' 123.8 128.5' 116.7 151.0 126.4' CHCI, 117
156 trans-3-Phenyl-4-benzyl- 168.0 49.3 44.9 129.2" 124.5 128.5' 116.6 150.6 124.1 CHC13 117
157 4-Methyl-5.7-dihydroxy- 168.7 37.0 24.9 1533 99.4 155.6' 96.2 158.1 107.2 CDC13 112
158 (See Scheme 1) 168.0 34.0 28.8 152.9 100.0 159.0 104.8 165.0 106.8 CDC13 112

Linear furanocoumarins c-2 c-3 c4 c-5 c-6 c-7 c-8 c-9 c-10 c-2' C-3 Solvent Reference
159 Psoralen (see Scheme 1) 161.1 114.7 144.2 120.0 125.0 156.6 99.9 152.2 115.6 147.0 106.6 CDC13 37, 39,46,
102,118
160 2-Thiono- 197.4 127.0 136.6 120.4 125.7 156.0 99.1 153.9 116.8 148.6 106.7 DMSO-d6 46
161 3-(l",l"-DimethylaIlyl)-(chalepensin) 159.2 132.4 144.9 119.1 124.0 155.2 98.2 150.2 115.3 146.0 105.9 CDC13 39,108. 118
162 3-(2",2"-Dimethylcyclopropyl)- 162.9 126.6 138.0 118.7 124.5 155.5 99.2 150.7 117.7 146.4 106.2 CDC13 108
(rutolide)
163 5-Methoxy-[bergapten) 160.3 112.8 139.4 149.6 113.0 158.5 94.0 152.7 106.7 145.0 105.3 CDC13 37, 39,46,
102. 118
164 2-Thiono-5-methoxy- 197.2 125.3 131.2 149.4 113.1 157.9 92.7 154.2 107.4 146.4 105.6 DMSO-d6 37.46
165 lsooxypeucedanin (see Scheme 1) 160.5 112.7 138.9 147.5 113.2 157.5 94.5 152.1 107.0 145.1 103.8 CHCI3 4
166 Oxypeucedanin (see Scheme 1) 160.3 112.3 138.5 i4i.a 113.5 157.4 93.8 151.9 106.6 144.8 104.1 CDC13 39
167 Prangol, aviprin (see Scheme 1) 160.4 111.8 139.9 149.1 113.2 157.6 93.0 152.1 106.4 145.4 105.5 CDC13 39
168 8-Hydroxy-(xanthotoxol) 160.0 113.7 145.3 110.1 125.2 145.3 130.1 139.8 116.2 147.2 106.9 DMSO-d6 4,37, 46
169 8-Methoxy-(xanthotoxin) 160.4 114.5 144.4 113.1 126.2 147.6 132.7 142.9 116.5 146.6 106.8 CDC13 4, 37,46, 108
170 2-Thiono-8-rnethoxy- 196.6 127.1 136.8 113.4 127.1 147.0 131.6 144.8 117.9 148.5 107.0 DMSO-d6 46
171 8-lsoprenyloxy-(imperatorin) 160.2 114.2 144.3 113.2 125.7 148.3 131.2 143.5 116.2 146.4 106.6 CDCI, 4, 37
172 2'-lsopropyl-(anhydromarmesin) 161.1 114.1 144.2 118.8 126.5 156.3 99.1 151.5 115.0 167.3 99.5 CDCI, 37,46
173 2-Thiono-2'-isopropyI- 197.2 126.7 136.7 119.2 127.0 155.7 98.6 153.6 116.5 167.4 99.9 DMSO-d6 46
174 5-Methoxy-8-hydroxy- 159.7 112.2 139.6 141.0 114.7 146.9 125.3 139.6 107.1 146.0 105.1 CDCl, 39,118
175 5,8-Dimethoxy-(isopimpinellin) 160.5 112.8 139.5 144.4 114.9 149.9 128.3 143.7 107.7 145.3 105.3 CDCI, 37, 39, 46,
102,108
176 5-Methoxy-8-acetoxy- 159.7 112.6 139.1 146.7 113.6 149.9 118.1 143.8 106.9 145.1 105.3 CDCl, 39,118
177 5,2",3"-Tribromoirnperatorin (see 159.0 115.8 142.1 127.7 115.5 146.4 130.6 143.7 106.3 147.1 107.3 CDC13 67
Scheme 1)
178 2'-lsopropyl-3'-methoxy-(peucedanin) 160.9 114.3 144.0 116.5 121.6 153.5' 99.8 151.5' 114.7 152.5" 136.3 CHCI, 4
179 4,8,2'-Trimethyl- 161.6 112.9 155.7 112.3 125.6 153.4 116.2 149.1 109.3 157.6 102.9 CDCI, 37
180 2',3'-Dihydro-5-methoxy- 161.5 110.5 139.2 152.7 105.9 165.5 92.9 156.6 110.4 72.4 28.3 CDC13 37
181 2',3'-Dihydro-2'-isopropenyl- 161.3 112.2 143.7 123.4 124.6 163.5 98.0 156.1 112.8 87.6 33.6 CDCI, 61
(ammirin)
182 Marmesin (see Scheme 1) 160.5 111.2 144.6 123.8 125.5 163.3 96.7 155.1 121.1 91.0 28.7 DMSO-d6 4, 37
183 Prantschimgin (see Scheme 1) 161.0 111.8 143.5 123.1 124.4 163.1 97.6 155.4 121.5 88.7 29.3 CHCI, 4
184 Rutamarin (see Scheme 1) 159.6 130.4 137.7 122.8 123.7 161.9 96.7 154.2 112.8 88.2 29.7 CDC13 108
185 Rutarin (see Scheme 1) 160.1 112.9 147.8 126.6 127.0 145.9 117.3 152.7 111.4 91.3 28.9 DMSO-d6 102

Angular furanocoumarins C-2 C-3 C4 C-5 C-6 C-7 C-8 C-9 C-10 C-2' C-3 Cd' Solvent Reference
186 Angelicin (see Scheme 1) 160.2 114.5 144.5 123.9 108.8 157.3 116.9 148.5 113.5 145.9 104.0 - CDCI, 48
187 Dihydrooroselone (see Scheme 1) 160.9 113.7 144.6 122.7 108.2 157.0 118.0 147.8 113.3 166.3 97.2 - CDCI, 48
188 Oroselol (see Scheme 1) 160.9 113.8 144.5 123.4 108.6 157.0 117.7 147.9 113.4 164.7 98.0 - CDCL 48

66 ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982

 13CNMR SPECTROSCOPY OF COUMARIN DERIVATIVES

Table 3. (Continued).
No. Name c-2 c-3 c-4 c-5 c-6 c-7 c-8 c-9 c-10 c-2' c-3 C 4 Solvent Reference
189 (See Scheme 1) 160.7 113.8 144.5 123.0 108.0 157.2 117.8 148.0 113.4 167.1 98.9 - CDC13 48
190 (See Scheme 1I 160.7 113.8 144.6 122.9 108.1 157.2 117.8 147.9 113.2 167.4 98.6 - CDC13 48

Linear pyranocoumarins
192 3-(l".l"-Dimethylallyl)-l91(see 160.0 131.0 137.6 120.1 118.0 154.9 103.3 154.5 112.8 77.5 129.2 124.0 CDCI, 119
Scheme 1)
193 5-Methoxy-(xanthoxyletin) 161.0 112.4 138.5 157.6 107.4 152.9 100.8 155.7 111.3 77.5 130.6 115.8 CDCI, 120
194 8-Methoxy-(luvangetin) 160.3 112.8 143.4 120.8 118.9 148.9 135.1 147.9 114.3 77.5 130.9 118.9 CDC13 39
195 3-(p-Methoxyphenyl)-4,5-dimethoxy- 161.3 111.9 164.1 151.5' 112.2 153.6' 113.3 150.5 104.5 77.1 130.6 115.6 -b 121
8-isopentenyl-
196 3',4'-Dihydro-3'-hydroxy-(aegelinol) 160.5 112.3 144.2 129.4 118.1 156.6 103.2 153.6 112.3 78.4 67.6 30.4 CDCI, 39
197 Clausmarin A (see Scheme 1) 162.4 130.3 137.9 123.0 124.3 159.8 96.7 154.4 112.7 84.0 87.2 30.5 CDC13 122
198 Clausmarin B (see Scheme 1) 162.6 130.3 138.2 122.9 124.9 160.2 96.8 154.4 112.7 75.3 74.2 32.0 CDC13 122
199 Xanthalin (see Scheme 1) 160.4 113.3 142.9 127.2 116.0 156.1 104.1 154.9 112.7 77.9 68.7 64.3 CDC13 4
200 Peuarenarin (see Scheme 1) 160.6 113.7 143.1 127.5 115.3 156.3 104.5 155.3 113.1 78.0 68.9 66.1 CDC13 4
201 Peuarenin (see Scheme 1) 160.3 113.7 143.0 126.8 114.6 155.9 104.5 155.2 113.1 77.7 69.9 65.9 CDC13 4

Angular pyranocournarins
202 Seselin (see Scheme 1) 160.4 112.2 143.5 127.5 114.6 155.9 108.8 149.8 112.2 77.2 130.4 113.1 CDCI, 39
203 3-(p-Methoxyphenyl)-4,5-dimethoxy- 161.2 112.1 163.9 154.9' 107.8 153.9" 119.9 147.4 103.8 77.4 129.7 114.3 -b 121
6-isopentenyl-
204 3',4'-Dihydroseselin 161.0 111.5 143.6 125.9 114.1 157.2 108.8 152.8 111.2 75.1 31.1 16.1 CDC13 39
205 3,6-Dichloro-3',4'-dihydroseselin 154.2 118.4 138.7 125.0 119.3 152.4 110.5 149.7 111.1 76.5 31.0 16.8 CDC13 39
206 3'cu-Hydroxy-4'~methoxy-3',4'- 159.4 112.9 143.0 129.1 114.1 156.7 107.2 153.8 112.3 78.5 73.7 68.6 DMSO-$ 39
di hydroseselin
207 (+)-Anomalin (see Scheme 1) 160.3 111.8 144.8 129.0 114.1 156.2 109.0 150.8 111.9 77.1 70.1 59.9 CDC13 39

c-2 c-3 c-4 c-5 c-6 c-7 ca c-9 c-10 Solvent Reference

208 Eriocephaloside triacetate: (see

Scheme 1) C-2 to C-10 159.1' 115.7 143.3 123.1 108.6 156.9 115.7 148.3 115.7 CDC13 123
c-2' to c-10' 159.1 103.3 160.6 126.3 114.2 159.4' 104.3 155.4 106.6
209 Aflatoxin B, (see Scheme 1) 155.2 117.4 177.1 161.6 90.9 165.8 107.9 153.0 104.0 CDCl3 43, 44

a In ppm downfield from tetrarnethylsilane (S=O).

Not reported.
May be interchanged.
Doubled data sets due to restricted internal rotation.

6m
l\

I
0
OH
40

Ro*omo 41 :R=H

42: R= Ac

Scheme 1

ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982 67

 H. DUDDECK AND M. KAISER

&
0 0

56 57 58

I R R'

&
66 H H s-s

67 H OCH,

\ O R
R' 68 H F

69 CH, H 71
70 C,H, H

126 CH,

127 n-C5H,,

I25

& HO OH
0
S

16 OH
108
98

Scheme 1. (Continued).

68 ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982

 I3C NMR SPECTROSCOPY OF COUMARIN DERIVATIVES

O ' y
I R R'
IR R'
132 CH, H

OH OH
I I' I
HO

mo
2'

7 \
8

159
I34 O '

*
YI58

Br

Br

177
0

OR

167
I CH,- CHOH - c (cH,), OH

R' R2 R3

182 H H H

R + - - ; 2 183 CO - CH = C (CH, )2 H H

184 COCH, C(CH,),- CH =CH, H

R3
185 H H p- D - glUCOSYl

ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982 69

 H. DUDDECK AND M. KAISER

R
po -
186
187
188
R

189
190

Configuration

J=JyJ 191
0
at C - 7 '

OR2
199 COC(CH3)=CHCHJ COC(CH,) =CHCH,

200 COC(CHJ =CHCH, CO-C(CHJ-CH(CHJ

0 '0'
201 COC(CH3) -CHCH, CO-C(CH,)-CHCH,

F o Po 0 4'

3'
202
OY O
''to?
&
207

209
OAc OAc
208
Scheme 1. (Continued).

70 ORGANIC MAGNETIC RESONANCE, VOL. 20, NO. 2, 1982

 l3C NMR SPECTROSCOPY OF COUMARIN DERIVATIVES
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Manske, Vol. XVIII, p. 217, Academic Press, New York
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13. F. Bohlmann, R. Zeisberg and E. Klein, Org. Magn. Reson.
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Received 18 February 1982; accepted 21 April 1982